Dyestuffs



Patented Oct. 2, 1945 STATES 2,385,815

DYESTUFFS John David Kendall and Douglas James Fry, 11-- ford, England, assignors to Ilford Limited, ll-' ford, England, a British company No Drawing. Application August 21, 1941', Serial No. 407,838. In Great Britain October 16, 1940- 15 claims.- (Cl. 260-240) This invention relates to the production of dyestuffs suitable for sensitising gelatino-silver halide photographic emulsions.

According to the invention, photographic sensitising dyestuffs are produced by condensing an alkyl or aralkyl quaternary salt of a compound of the general formula I pound containing either a reactive thioether or seleno=etlier group (including an a'ryl alkylor afalkyl=thioether or Selena-ether group) or a--(CH CH)'m.NH group where m is 1, 2 or 3 (including N-acyl, N-aryl and N-acylaryl substi= tuted groups of this type) in the u or '7 p sition to the quaternary nitrogen atom.

The grouping (CH=CH)m.NHz is hereinafter referred-to as the aminovinyl type of group.

The alkyl or aralkyl quaternary salt of the compound of general Formula I may be, for example, a methyl-, ethylor higher alkyl, or benz'yi or naphthyl-niethyl chloride, bromide, iodide, sulphate or perchlorate. Preferab1y','liov'vever, it is an alkyl-p-toluene sulphonate compound and this may most convenientlybe produced by fusing a compound of general Formula I with an alkyl-p-toluen'e sulphonate, e. g. methyl or ethyl-'p-toluene sulphohate.

The group A may be, for example, an oxygen atom or an -NR group where R5 is a hydrogen atom or an alkyl, aryl, aralkyl or heterocyclic o s.

" Asiridicat-d above, R1,-

Rt, R4 and R5 may be alkyl or arallr'yl groups; examples are methyl, ethyl, propyl, but-yl and higher alkyl groups, ben 2y! and na'pnthypmethm groups. R2; R5, R4 and thiazole', thiazoline, oxazole, oxazoline, selenazole,

selenazoline, pyridine, quinoline, indolenine, diazine (e. g. pyrimidine) thiodiazole or quinazoline nucleus, including the cofresponding'substituted or unsubstituted polycyclic'nuciei such as-thebeiizthiazole, na hthathiazole and anthratinazole nuclei and also the nuclei of the dia'zines de scribd in British PatentNo. 425,609.

The production of compounds of the general Formula I may be effected by various processes,

e g. the process as described in application S. No. 291769, filed October 3, 1939 now 11.. s. Patent No. 2,265,908,-grafitd December-'9, 1941, in application S. N6; 331,674, filed'April 25, 1940, and

in application S. NO. 407,841- flld OII 'evendate herewith.

Any of the known types of heterocyclic quaternary nitrogen compounds containing the specified reactive thio-ether, selenoether or aminovinyl types ofgrou s' commonly employed inthe manufacture of cyanine .dyestufis' maybe employed in the present invention. Examples are the quaternary salts of the various heterocyclic compounds listed above.

The general course of the chemical reaction underlying the process of this invention may be set out as follows. The initial quaternary salt of the compound-of general Formula I-the alkyl or aralkyl salt used in forming the quaternary salt being designated as RsX -has the formula: (II)' I which is tautomeric with:

Assuming for the sake of simplicity of explanation that the quaternary salt has the Formula II, the condensation reaction where the second reagent contains. a reactive thioether group and the quaternary.='alkyl or, aralkyl salt, group is an RvY group, proceeds as follows:

-It will be, appreciated that byassuming the alternative Formula for the intial quaternary salt aslightlydifferent formula for the product 'is obtained and it is to be understood that the products may have a formula different from, but 'tautomeric' with, the formula set forth above.

If, instead 'of' a thioether type of group,vthe second'reagent contains a reactiveraminovinyl type of. group, in general Formula IV above by the addition of one or more pairs of methinegroups' between the added nucleus andthe .ll a

or has a formula which is tautomeric with the above.-

In the foregoing formulae, D2 represents the residue of a heterocyclic nucleus, e. g. one of those mentioned above, R6 and R-z are alkyl gr aralkyl the'product differs from that shown groups and X and Y are acid residues and n is nought or 1. Other symbols have the meanings previouslyassigned to them. V

In carrying out the process of this invention, it is not always necessary to isolate the quater- Vnary salt of the compound of Formula I. ll'hus by condensing a compound of the general Formula I with the desired second heterocyclic nitrogen compound and suflicient alkyl salt or aralkyl salt to convert both compounds to quaternary salts, the reaction may be effected in one stage.

mereisufficiency is employedzli H I Again, since the initial compound of general Preferably an excess ofalkyl or aralkyl salt over Il'ormula I may be prepared by condensing a suitable intermediate with a quaternary salt of a' heterocyclic nitrogen compound as described in application SLNo. 331,674, the formation of those 7 Y fidyestufis. lof the; present invention in which of the three .nuclei one is a pyrazolone nucleus and the other two are of the same nature as one 7 another, e g; both b enzthiazole nuclei, may be 'effe'cted'ina single operation by condensing togather a suitable pyrazolone derivative of the I r V V a r grouping of 'the residue of the initial compound;

type described in application S. No. 331,674, eag a compound of the general for'mm (R2, R3, R4 and R5 having the meanings assigned. to them above) two molecular equivalents of a I heterocyclic compound containing a reactive thjio ether, solenoether 0r aminovinyl type of group and a sufficiency of an alkyl salt or an arlkyl salt.

It will be understood that in the processes described in each ofthe two last preceding paragraphs, the initialgquaternary salt of the com:-, pound of Formula I-necessary to the process oi. this invention is formed during the reaction, and. reactswith the secondary reagent in the manner set forth above. 4

Thecondensation process of the invention is preferably'completed in thepresence of an: acid binding agent, e; g. pyridine, piperidine, -tri-- ethylamine, sodium acetate or potassium" carbonat'e. Where the heterocyclic nitrogen come. pound contains a reactive aminovinyl type, of group, the condensation is preferably completed in the presence of amalcoholic solution of'sodium acetater- I g, 1,, 'IT The following examples illustrate the .inven' Example I 0;38 gms. of u-(2-methyledihydrobenzthiazolylidene) -1:4 isobutylidene-1'-pheny1. 3'f-methyl 5'-pyrazolone, 0.62 gms. of :l -methylthiol-benzthi-r azole and 1.5 gms; of methylp 1301116118 sulphonate were mixed and heated together to? four hours at 140 C. on anoil bath. The mixture was cooled and there was then added 10 cos. of ethyl alcohol and 0.8 gms. of anhydrous sodium acetate. The mixture wasthen refluxed for twentyminutes and then poured into potassium bromide solution. The resulting mixture, after dilution with water was filtered to collect the precipitated" dye, the precipitate being washed withalc'ohol and ether. On recrystallisation from ethyl alcohol; the product was obtained as green crystals, melting at 230 C. with decomposition. This dyestuflf included in a g'elatino silver bromide photographic emulsion imparts a band of sensitivity extending to about 6700 A, with a maximum at about 6200 A I remote .II Preparation or the dyestuffs of the probable Iormul'a:-

Ha I

0.36 gm.- of 2methyldihydrobenzthiazolylidene 1:4'-i-so propylidene=l'phenyl=3' methyl+5' py razolone, 0.6 gm. of 1emethylthiol-benzthiazole and 2.0 gms. of ethyl-p-toluene sulphonate were fused together for three-hours at 140 C. on an oil bath. The mixture was then cooled and there was then added cos. of ethyl alcohol and 0.8gm. of anhydrous sodium acetate. The mixture was then refluxed for twenty minutes, poured into potassium iodide solution and diluted with water. A sticky precipitate for'nfnad, which hardened on treatment with spirit. The precipitate was boiled with methyl alcohol, filtered, and washed with methyl alcohol, hot benzene and ether. The product was thus obtained as green crystals having a gold lustre, melting at280 C. with decomposition. g M

This dyestuif is a powerful sensiti'ser; when incorporates in a geiatin'o silver bromide photo-' graphic emulsioii'itimparts" a. bandof sensitivity extending t about 6800A with a'sharp maxi-mum at about 6300K. V

Preparation of the oyeeturr or the probable formine:-

I. c-om Gr'Hi I 'azole ethio'dide and 10 cos. of pyridine.

formed was separated by filtration and washed with ethyl alohol arid" ether. Orl recrystallisation from methyl alcohol the product wa obtaiiied: as olive green needles, melting at 248 C. with decdir'ipos itidn. This dyestuff when incorporated in a gelatino silver bromide photographic emulsion imparts aband of sensitivity extendmemo about 6500A with a maximum at about 6200 A. Example IV Preparation of the dyesrurr or the probable formula: V

CE: /CH: s o

1 gm. of 2 methyldihydrobenzthiazolylidene- 1.4'-iso" propylidene-l' -'phenyl'-3'-methyl- 5'-py-* razolo'ne and 3- gms. of methyl-'p-toluene. sulphonate were mixed together and heated for three hours at C. The cooled mixture was then dissolved 'in- 20' cos. of ethyl alcohol and poured into potassium iodide solution. Th quaternary salt thus formed crystallised out on'standing and was removed by filtration and washed with ethyl alcohol and ether. It consisted of yellow needles melting at 249 C. with decomposition.

0.49 gm. of thequaternary salt prepared as above, 0.45 gm.- of 2-w-acetanilidovinyl-3.3-di methyl-indolenine methiodide and 7.5 cos. of pyridine were mixed together and heated for four hours on a water bath. The solution was then poured: into potassium i'odidesolutio'n and diluted with water. The dyestufi separated on standing and was removed by filtrationand washed with marn'at about 6800 A.

Example V Preparation of the dyestufi of the probable formula: I

0.5 2 gm. of 2-methyl-dihydrobenzthiazolylidene- 1.4 isopropylidene-1f-phenyl 3-methyl-5--pyrazolone and 3 gms. of methyl-p-toluene sulphoriate were heated together for one hour at 160 C.

The mixture was then coole v and there was then adde'0.62 gm. of 1-w-acetanildovinyl benZ-thi- The mixture" was then heated on a water bath forone hour, poured intopotassium iodide solution and diluted with water. Solid separated out' and was removed by filtration. On recrystallisation of this 'solid from methyl alcohol, impurities first 'rys'tallisir'ig Wr filtered off; the filtrate was about 700 A..

then concentrated and yielded the desired dye-1 stuff 'asdark green'crystals, .melting at 194 C.

with decomposition. (Instead of using ccs.,of pyridine a set forth above there may be emp1oyed'10 ccs. of ethyl alcohol containing 0.8 gm. of sodiumacetate). This dyestufi when incorporated in a gelatino-silver bromide photo-e graphic emulsion imparts a band of sensitivity between 6800 A and 7400 A with a maximum at 1.2 girls. :-of 2-methyldih'ydrobenzthiaolylidene- 1.4 L isopropylidene-1 -phenyl 3'-methyl-5-pyrazolone and 1.2 'gms. of 2-mthylthiol-quinoline V and 6' gins. of ethyhp-toluene sulphonate were mixed together'and heated for 2 /2'hours at 140? C. The-mixture was then heated for a further half-an h'our at 170- C. and then cooled. Thereupon, 10 cos. of pyridine were added and the mix- 'ture heated first for one hour on a Water bath and then under reflux for 1 /2 hours. The solution' wasthen poured into potassium iodide solution and diluted'with water. The dyestuff crys-: tallised out and was separated by filtration and washed with ethyl alcohol, ether and hot benzene. On recrystallisation from ethyl alcohol the prod not was obtained as bronze crystals melting at 197 C;-with decomposition. This dyestufi when incorporated in a, galatinosilver bromide'photographicemulsion imparts-a, band of senstivity extending to about 7200 Awith a maximum at Example VII Preparation of the dyestuflf of theprobable formula: V V 7 I f CCH3 CgHs CtHs C2 5 1.2 gms. of 2 methyldihydrobenzthiazolylidene- 1.4 isopropylidene-1-phenyl-3-methyl-5'-py razolone, 1.1 gms. of 1-methylthiol-benzoxazole and 5 'gms. of ethyl-p-toluene sulphonate were mixed and heated for six hours at 160 C. The mixture was then cooledvand 15 ccs. of pyridine were added. The mixture was then refluxed for halfean hour, poured into potassium iodide s0 lution and diluted with water. The dyestuff separated out and was removed by filtration and washed with ethyl alcohol, 'hot benzene and ether. On recrystallisation irom'. methyl 31100! hol, the product was obtained as small gold crystals melting at 198 C. with decomposition at above 210 C.. This dyestuff when incorporated in a g'elatino silver bromide, photographicemul:

sion imparts a band; of sensitivity extending to about 6300 A with a maximum at about, 6000 A.

formula:

.CHs

0.95 gm. of 2 methyldihydrobenzthiazolylidene- 1:4'-isopro pylidene -'*3' methyl-isoxazolone, 1.2 gms. of. l-methylthiolbenzthiazole and; 5 gms. 0f methyl-p-toluene sulphonate were heatedeto gether for 2% hours at 160 C. and then cooled.

20 ccs. of pyridine were then added to the mixture and the mixture refluxed for half-an-hour. V

and then poured into potassium-iodide solution.

The dyestufis separated out and was removed by filtration and washed with ethyl alcohol and ether. On recrystallisation from methyl alcohol the product was obtained as-purple crystals, melting at 242 C. with decomposition. This dyestufi when incorporated in a, gelatino silver bromide photographic emulsion imparts a band I of sensitivity extendingwoabout 6700 A- with a sharp' maximumatabout'6500 A' r a 1 P eie q formula;

. li CH1.

0.2 gm. jor 2-methyle-dihydrobenzthiazolylidene 1 4..-isopropy1idene-1' -phenyl-.5 pyrazolQne, 0.21 gm. of lmethyl .thiol-benz'thiazole and.1.5 ems. of. methyl p to1uene sulphonate were .mixed and heated together for three hours at.16,0 :C. The mixture was cooled, l5 cos. of. pyridine were added, and the mixturewas' then warmed forfifteen nut on, zwat bath a d: --m luxedv f thirty. minutes. The mixture was then poured into water, filtered and a solution of potassium bromide-was then added to the filtrate-whereupon thedesired dyestuif separated out and was removed by filtration. This dyestufi was boiled out with benzene, filtered and washed with ethyl alcohol. It consisted of green crystals melting at 243 C. with decomposition.

This dyestuff when incorporated in a gelatinosilver bromide photographic emulsion imparts a band of sensitivity extending to about 6800 A with m'axima: at about-moon and'6600 A r tor "the dyestufl' of. ro able tion of a quaternary salt of the secondary reagent and the condensation of the two quaternary salts to form a dyestufi of this invention. 5.3 gins. of 1-phenyl-3-methy1-4-isopropylidene- 5-pyrazolone, 13.6 gms. of l-methylthiol-benzthiazole and 30 grams of methyl-p-toluene sulphonate were mixed together and heated for three hours at 130-140 .C. Themixture was then .colled, 100 s. of pyridine were added, and. the mixture was heated first for ten minutes on a. water bath and then for thirty minutes under reflux. The solution was then poured into potassium iodide solution. The dyestufi separated from the cooled solution and was removed by liltration and washed with ethyl alcohol and ether, followed by recrystallisation from methyl al- The following are examples of additional dyestuffs which may be made by the general processes indicated in the preceding Examples 1-10. In all these examples the parts given are parts by weight. 7 a Example XI 1 Preparation of the dyestufi of the probable formula: v I

Example XII Preparation of the dyestufi' of the probable or-mula: I

This dyestuif was obtained by reaction between 1.07 parts .1-pheny1-3-methyl-4-isopropylidene-5- pyrazolone, 3.63 parts 1 methylthiol-4:5-.-dimethoxy-benzthiazole and 6 parts ethyl-p-toluenesulphonate. The dyestufi was converted into the iodide salt by pouring a solution of it into potassium iodide solution. It consisted of emerald-green crystals melting at 285 C. with decom-, position. Incorporated in'a gelatinosilver iodobromide emulsion it imparts a band of sensitivity extending to 7100 A with .a maximum at 6700 A.

5 xa ple XII Preparation of the dyestuir or the probable formula:

, C=CH-C=CHC o1. .01

N N I C-CH 6,11. 0,41 -1 l Cum 01H| 1 This dyestuif was obtained by reaction between 1.07 parts 1-pheny1-3-methyl-4-isoproplyidene-5- pyrazoline, 4.31 parts l-methyl-thiol-l-chlorbenzthiazole and 6 parts of ethyl-p-toluene-sulphonate. .The dyestufi was convertedinto iodide salt by pouring a solution unit into potas sium iodide solution. It consisted of bronze crystals melting at 233 C. with del omposition, Incorporated a. gelatino silver iodorbrgmide emulsion it impartsa .band .of sensitivity extend? ing'to 6500 .A with a maximumaat 6.2.0.9 A.- a

Example XIV This dyestuff was obtained by reaction between 2.14 parts ''l phenyl 8 rnethyl -4-isopropylidene 5-py1jazolone,-6-.6 parts f1-methylthiol -benzoxazole and 15 parts methyl p-toluene sulphonate'. The dyestuff was converted'in-to thew iodide-salt by pouring a solution of it into potassium iodide solution. It consisted of scarlet crystals Lmelting at 270 C. with decomposition. Incorporated in a gelatino silver iodo bromide emulsion it imparts'a band, of sensitivity extending to 6100- A with amaximum at 5700 Y Example XV of the dyestu'fi oi the probable for- Preparation mula: Y

ame xvi" repai-ationof the dyesuirt of the probable for mula:

This dyestufi was obtained by reaction between 0316 part 3-inethy1 -4'-isopropylidene-5;isoxazo+ 1one, 2.31 parts l-methylthiol-S:G-naphthathiazoleand i parts'ethyl p-toluene sulphonate. It consisted of green crystals melting at 248 C. with assists decomposition. Incorporated in a gelatino silver iodo-bromide emulsion it imparts a band'of sen- A with'a maximum at sitivity extending to 6750A.

' 'M;Exdmple'vXVIIiv 1533-11,; Preparation of the dyestufi of the probable mula; V p

fer:

0.7 part '3emethyhg isopropylidene diso cazolone, 3.5 parts l-methylthiol-benzoxaz'ole and. {i parts 'methyl -petoluene-sulphonate. The ye stufil'wasconverted V w pouring asolution ofit into potassium perchlorate solution lt consi ste d =o f orange crystals melting This dyestufi wasobtained 'by reacti'on between "1.07 7 parts 1-phenyl-3 methylA-isopropylidene- '5-py'razolone', 3,3;pa'rts l-methylthiol-benzoxazole and 8 parts ethyl-p-toluene sulphonate. The dyestuff was; converted into the perchlorate salt by pouring a solution of it intopotassium perchlorate solution. *It' consisted: r scarlet crystals melting" at 285. C. with decomposition; Incorporated in a gelatino' jsilveri iodo -bromide emulsion it imparts a band of sensitivity egztending to 6000 A with a maximum at 5700 A. e I l the perchlorate 'Isaltby 7 Example XIX v v Preparation ofthe dyestufi of the-probable formula: v a r 1 7.; :flCHa CH: or hug-g H 1 v This dyestufi. was obtained by reactionbetween 0.9 part u-(l:3:S-trimethylindolylidene) -meth.- yl-2:4-butenylidene-3-methy1 5' isoxazolone, -2.7' parts l methylthiol benzthiazole and 4.5 parts methyl-p-toluene sulphonate. The dyestuff'was converted into the perchlorate salt by pouring a solution of it intqpotassium perchlorate solution. It consisted of bronze crystals melting at 200 C. with decomposition. Incorporated in a gelatino silver iodo-bromide emulsion this dyestuff impartsa band of sensitivity with a. maximum at about 6700 A. i a

Example XX Preparation of the dyestuff of the probable formula;

2.06 parts 2-ethyl- 51's naphthathiazolylidene- 1:4 isopropylidene-3-methy1-5-isoxazolone and 5 parts methyl-p-tolue'ne sulphonate were mixed together and fused for three hours at 130-150 C. The product'was cooled, dissolved in ale'ohol and then poured into'potassium iodide solution. The quaternarysalt thus obtained was washed with alcohol, and 0.98 part thereof were-added to a fusion mixture of 0.5 part N'-ethyl-quino'- line-4-thione and 0.6, part ethyl-p-toluene sulphonate. 15 cos. of'e'thyl alcohol were added and :the pmixturerefluxed gentlyior 25 minutes.;. The mixture was then poured into potassium-iodide solution and the 'dyestufi was separated by filtration; and recrystallised. It consisted of apurple' powder melting at 203 C.fwith decomposition. Incorporated I in a 'gelatifio silver iodo-brqmide 'emulsion'it imparts a band of sensitivity'ezitend ing to 7600 A with a maximum at 6900 A.

' Example XXL Preparation of the-dyestufi of the probable formula: 7 a s V This dyestufi was --mixed together and boiled and 0.1 part of .anhy.-

"ing to 8600 041 part 2 methyldihydrobenzthiazolr ide e 1:4 isopropy ene-i'-phenrl 3'- ury fy a olone, 0.56 part l-methylthiolbenzthiazole and 2 parts ethyl-r-t u sulph natea The dy stufi was converted into the bromide salt by pouring a solution of it intopotassium bromide solution. It consisted of purple crystals melting at 2514 "C. with decomposition.

Errample XXII Preparation of the dyestufi of the probable formula:

an. on,

0.5 partofthe quaternary salt prepared as in Example IV 0.43 part .of 4-.acetanilidovinyl quinoline methiodide and: 4 parts :ethyl alcohol were 25 drous sodium acetate was added. The whole mix- 'ture was refluxed forten minutes-and rthen poured into potassium iodide solution. The dyestuff separated and was obtained-as deep blue crystals melting at 205 C. with decomposition. Incorporated in a vgelatino-silver iodos'bromide emulsion-it imparts a band of sensitivity extend- A with maxima at about '1500 A and 8100A.-

i -Ezrample XXIII I 5&5 Preparation of the, cye tuir r the'pro'bable This dyestufi was prepared as in Example XXII but using 0.44 partof 4-acetanilidovinyl quinoline ethiodide in place of th methiodide. The dyestuff was obtained as golden crystals melting at 186 C. with decomposition. Incorporated in a gelatino silver iodo-bromide emulsion it imparts a band of sensitivity'with a maximum at about 0.3 part of -1-(2-methyl-dihydrobenzthiazolylidene) -1 :4 -isobuty1idene-1 -pheny1 a3 methy1- 5'- -azolone, 0.5 part of l-methyl thiol benz 70-- thiazole and 1.5 parts of 'methyl p-toluenesulphonate were mixedtogetherandheated for two hours at 120-130 C. The mixture was then cooled and'refluxed with 10 parts of pyridinefgr 45 minutes and then poured into potassium iodide .1

solution. The product separated out and removed by filtration, and. washed with ethyl al c hol and eth r. It was obtained as olden c y tals melting at 285 C. r

In the following claims, the expression (thieether group, seleno-ether group and amino- -vinyl group have been used for the sake of briefness but it is to be understood thatthe first-two of these expressions include the corresponding aryl-, alkyland aralkyl-thioether and selenoether groups and that the third expression includes groups of the formula .(CH.=CH)m.NI-I 2, (where m is 1, 2 or 3) and includes N-acyl, N-aryl and .N-acylaryl substituted groups orthis type.

What we claim is:

1. Process for the production of dyestufis which comprises condensing a compound selected from the group consisting of the alkyl and aralkyl quaternary salts oi compounds of the general formula:

where R1 is selected from the group consistingof alkyl and aralkyl groups.

R2 and R4 are selected f om the group consisting of hydrogen, allgyl, aryl and aralkyl groups,

R: is selected from the group consisting of hydrogen. alkyl, aralkyl, aryl and heterocyclic groups,

A is selected from the group consisting .of the divalent oxygen atom and divalent NR agroups, where R5 is selected from the group con sisting of the hydrogen atornand monovalent hydrocarbon radicals D1 is the residue of a heterocyclic nucleus of the type used in cyanine dyes n is selected from the group consisting of 0 or 1 and l m is selected from the group consisting of 0, 1, 2 and 3, with a second quaternary salt of a heterocyclic nitrogen compound of the type used in cyanine dyes containing a reactive group selected from the group consisting of the reactive .thiO- ether, selenoether and aminovinyl types vof group,

in a position relative to the heterocyclic nitrogen atom selected from the group consisting of the and '1 positions.

2. Process for the production of dyestuffs which comprises condensing a compound selected from the group consisting of the alkyl and aralkyl quaternary salts of compounds of the general formula: v

where R1 is selected from the group consisting of alkyl and aralkyl groups,

R2 and R4 are selected from the group consisting of hydrogen, alkyl, aryl and aralkyl groups,

R: is selected from the group consisting of hydrogen, alkyl, aralkyl, aryl and hetcrwyclic groups,

D1 is the residue of a heterocyclic nucleus of the type used in cyanine dyes,

n is selected from the group consisting of 0 and 1 and I 1 se e ted 1m th rou 'sons siilie lig r en atom. 1. 1 4. Process for where is selected from the group of'alkyl and aralkylgroups;

' of the a and 1 positions. j

2 and 3, with a second quaternary salt of a heterocyclic nitrogen compound of the'type used in cyanine dyes containing areactive group selected from the'group consisting of the reactive thio' ether,selenoether and aminovinyl types of group, in a position relative to the heterocyclic nitrogen atom selected from the group consisting ofthe -oc and'y positions.

- 3. Process according to claim 2 wherein the second quaternary salt contains a- CH3S- group in a position selected from the group consisting of the wand 'y-positions-to the heterocycliclnitro comprises condensing a compound 'selectedfrom the group'consisting of the alkyl andaralkyl qual ternary sa'lts ofcompounds of the general forconsisting R2 and R4 are selected from-the group consisting'ofhydrogen, alkyl, aryl'and aralkyl groups, R3; and Rs'are selected fromthe' group-con- Siding hydrogen, r ia a r aryl and heterocyclic groups a 7 I D1 is the residue of a heterocyclic nucleus of the type used in cyanine dyes,

nf isfselected from' andl and j a: is selectedfr'om 1p, 2 and 3, with a secondary quaternary salt of a heterocyclic nitrogen compound of the type used in 'cyanine, dyes containinga reactive group selected from'the group consisting of the reactive thioether, selenoether and aminovinyl types-of group, in a positionrelative' to the heterocyclic nitrogen atom selectedf rom' the group consisting 5; Process according to claim'e wherein the second quaternary salt contains a CH3S''gr0up in a position selected from the group consisting 'of the wand 'y positions to the heterocyclic nitrogen atom. I p 6. Process for the production of dyestuffs which comprises condensing a'c'ompound of the general where R1 is selected from the group consisting of 7 alkyl and aralkyl groups,

R2 and R4 are selected from, thegroup consisting of hydrogen, alkyL'aryland aralkyl groups, R3 is selected from the group consisting ofjhydrogen, alkyl," aralkyl, aryl" and 'hetero'cyclic groups,

i "'2 and 3, with a heterocyclic nitrogen compound of the type used in cyanine dyes containing a reactive'group selected from the group consisting the production of dyestufis'which' asses of the reactive thioethergselenoether and-amino vinyl types of group, in a position relative to the salts.

7. Process for the production of dyestuffs which comprises condensing a compound of the general 7 formula: V

, V w lg --.--D1---;----; If; m, I 1%I-(c =cH);=(cHQH= ;co=c-- R, R1 '02 N I N Q 7 g V '7 V where R1 is selected from the group consistin of alkyl and aralkyl groups, R2 and R4 are selected from-the group consistingofhydrogen, alkyl, aryl and aralkyl groups, R3 and R5 areselected from the group consisting of hydrogen, 'alkyl, aralkyl, aryl and heterocyclicgroups; y; r V

D1 is:the residue of a heterocyclic nucleus of the type used incyanine dyes, 1

v u the group" consisting of f 0 r the group consisting ofQO,

n is selected ,from the group consisting of andland a is selected from the group consisting of:0,'1, 2 and 3 ,with. heterocyclic nitrogen compound of the type used in cyanine dyes containing a reactive group selected from the group consisting of the reactive thioethenselenoether and amino vinyl types ofgroup in a position relative to the heterocyclic nitrogen atom selected from the group consisting of the a and 'y positions, in the presence of a sufiiciency of a salt selected from the group consisting of alkyl and aralkyl salts to convert both thesaid compounds to quaternary salts.

8. Process for the production of dyestuffs which comprises condensing :together one molecular equivalent of a mula:

(where R: and R4 are selected from the group consisting of hydrogen, alkyl, aryl and aralkyl .groupsand-Ra and Rs are selected irom the group consisting of hydrogen, alkyl, aralkyl, ,aryl and heterocyclic groups) and two molecularequivalentsof a second heterocyclic nitrogen compound of the type used in cyanine dyes containing a reactive group selected from the groupconsisting of thereactive thioethen'selenoether and amino vinyl types of group in a position relative to the heterocyclic nitrogen atom selected from the 7 group consisting of the vi and '1 positions, in the presence of a sufficiency of a salt selected from the group consisting of -alkyl and aralkyl salts to convertall the said compounds to quaternary ix-fz, ,1 V Z 9. Process. according to l claim 8 wherein the second heterocyclic, nitrogen ,.compound contains a CH3S.- group in a;position;s elected from the group consisting of the a and 'v positions to'the heterocyclic nitrogen atom a i f compound ofthe general fori ass sts where R1, R6 and R7 are selected from the group consisting of alkyl and aralkyl groups, '1

R2 and R4 are selected from the group con- I sisting of hydrogen, alkyl, aryl and aralkyl groups,

R3 is selected from the group consisting of hydrogen, alkyl, aralkyl, aryl and heterocyclic groups,

A is selected from the group consisting of the divalent oxy en atom and divalent --NR5 groups, where R5 is selected from the group consisting of the hydrogen atom and monovalent hydrocarbon radicals,

D1 and D2 are residues of heterocyclic nuclei of the type used in cyanine dyes,

X is an acid residue,

12 is selected from the group consisting of and 1 and 3 a: is selected from the group consisting of 0, 1,

2 and 3, and dyestuffs having a general formula tautomeric therewith.

. 11. Dyestuffs of the general formula:

where R1, R6 and R1 are selected from the group consisting of alkyl and aralkyl groups,

R2 and R4 are selected from the group consisting of hydrogen, alkyl, aryl and aralkyl groups,

1, 2 and 3 and dyestufis having a general for- 60 mula tautomeric therewith.

12. Dyestuffs of the general formula:

where R1; R6 and R? are slect'edfroni the group consisting ofalkyl and aralkyl groups,

R; andvRe are selected from the group consisting of hydrogen, alkyl, aryl and aralkylgroups,

R3 and Rs are selected from the group consisting of hydrogen, alkyl, aralkyl, aryl 'and heterocyclic groups,

D1 and D2 are residues of heterocyclic nuclei of the type used in cyanine dyes,

2 and 3, and'dyestufi's havin" ageneralforinula tautoinerictherewithi I} 13;"Dyestufrs of the generai grams: 1

c I l o where R1, R6 and R7 are selected from the group consisting of alkyl and aralkyl groups,

R2 and R4 are selected from the group consisting of hydrogen, alkyl, aryl and aralkyl groups, R3 is selected from the group consisting of hydrogen, alkyl, aralkyl, aryl and heterocyclic groups,

A is selected from the group consisting of the divalent oxygen atom and divalent NR5- groups, where R5 is selected from the group consisting of the hydrogen atom and monovalent hydrocarbon radicals,

D1 and D2 are residues of heterocyclic nuclei of the type used in cyanine'dyes,

X is an acid residue,

n is selected from the group consisting of- 0 and 1 and a: is selected from the group consisting of 0, 1, 2 and 3 and dyestuifs having a general formula tautomeric therewith.

l4. Dyestuffs of the general formula:

where R1, R6 and R1 are selected from the group consisting of alkyl and aralkyl groups,

' R2 and R4 are selected from the group consisting of hydrogen, alkyl,'aryl and aralkyl groups,

R3 is selected from the group consisting of hydrogen, alkyl, aralkyl, aryl and heterocyclic groups,

D1 and D2 are residues of heterocyclic nuclei of the type used in cyanine dyes,

X is an acid residue,

n is selected from the group consisting of 0 and 1 andx is selected from the group consisting of 0, 1, 2 and 3 and dyestuffs having a general formula tautomeric therewith.

15. Dyestuffsctthe general'f ormulaz V 4-"."' .t"-"1".

cyclic groups,

D1 and D2 are residues of heterocyclic nuclei of the type used in cyanine dyes,

1 --i r"-""- I J v 1 1-, cn=cn).=ccncn=: ;cc=0-c-m X18 an and resldue I e R n is selected from the-group consistmg of 0 and 1 and c c A Q a: is selected from the group consisting'of 0, 1, N X 10 2 and 3 and dyestufis having a general formula.

v tautomeric therewith. w here R1','R and R1 are selected from the group JOHN D AVID KENDALL DOUGLAS JAMES FRY.

consisting of alkyl and aralkyligroups,

R2 and R4 are selected from the group conslst 15 i A N v ing of hydrogen, alkyl, and and aralkyl groups,

R3 and Rs are selected from the group consiting 01 hydrogen, alkyl, aralkyl, aryl and hetero- 

